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1.
C. Harrats  P. Moldenaers 《Polymer》2004,45(24):8115-8126
The phase morphology developed in immiscible polypropylene (PP)/polycyclohexylmethacrylate (PCHMA) blends has been studied using an in situ reactively generated polystyrene-graft-polypropylene compatibilizer from maleic anhydride grafted polypropylene (MA-g-PP) and amine end-capped polystyrene (PS-NH2) reactive precursors during melt-blending. The imidation reaction responsible for the formation of the compatibilizer is similar to the reaction occurring in polyamide/MA-PP (MA-EPR or MA-EPDM) blends which are industrially important. In the present blend PP/PCHMA/(PP-MA-PS-NH2), no undesired reaction occurs between the maleic anhydride groups and the backbone of the PCHMA chain, as is usually the case with polyamide homopolymer. This type of reaction, although considered non significant, has consequences on the phase morphology development as it affects the viscosity of the polyamide matrix when chain scission takes place. PP/PCHMA blends covering the whole range of compositions were prepared. The composition window at which the blends exhibit a droplet-in-matrix phase morphology and that where the two phases are co-continuous were determined using a selective phase extraction in combination with scanning electron microscopy. The generation in situ of the PP-g-PS compatibilizer substantially changed the state of the phase morphology developed. In the blends having a droplet-in-matrix type of morphology, the particle sizes were significantly reduced (by a factor of more than 10). Two types of MA-g-PP reactive copolymers differing in maleic anhydride content (1 and 8 wt%) have been separately employed with the same grade of PS-NH2. Emphasis was put on a detailed investigation of the behaviour and structural stability of the blends exhibiting a co-continuous phase morphology when the compatibilizer is generated. Significant differences were found in relation to the maleic anhydride content of the MA-PP reactive compatibilizer precursor.  相似文献   

2.
The present work describes the anisotropy and instability observed upon the formation of co-continuous phase morphologies in model polystyrene/polypropylene melt-extruded blends. Uncompatibilized and reactively compatibilized blends using amino-terminated polystyrene, PS-NH2, and maleic anhydride grafted polypropylene, PP-MAh, reactive precursors were investigated. Differences in phase morphology are discussed based on the viscoelastic properties of the components used, the blend composition and, the type and content of the compatibilizer precursor employed. As expected, for the same polystyrene grade at a concentration in the blend below 20 wt%, a polypropylene matrix having a higher viscosity enables the formation of a more co-continuous phase morphology than a less viscous one, as quantified by solvent extraction. The co-continuous phase morphology developed was found to exhibit a highly elongated structure upon melt flow through the die of the extruder. Isotropic co-continuity, observed inside the barrel of extruder, was transformed into anisotropic phase co-continuity in the form of interconnected infinite strands of the minor phase highly oriented in the extrusion direction.When the blends were thermally annealed, a 50/50 PS/PP co-continuous blend exhibits a substantial phase coarsening from micro- to millimeter scale without alteration of the phase co-continuity. The reactive compatibilization of the polypropylene and the polystyrene phases using 5 wt% PP-graft-PS, reactively in situ generated was able to significantly retard the phase evolution process.  相似文献   

3.
Polypropylene/polyamide 6 blends were prepared by melt mixing, without or with the addition of a suitable commercial product, a polypropylene grafted with 1% maleic anhydride, used as an interfacial modifier. The oxygen permeation through their films was studied as a function of temperature and the effect of the presence of the compatibilizer on the barrier properties of the material was examined. In addition, the diffusion coefficients were measured. The relationships between transport parameters and blend morphology were investigated by microscopic observations, together with chemical etchings, and a simple model was applied for interpreting the experimental permeation data. Differential scanning calorimetry was used in the determination of the degree of crystallinity of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1941–1949, 1999  相似文献   

4.
This work reports on morphological, mechanical, and micromechanical properties of polyamide 6 (PA 6), a styrene‐acrylonitrile copolymer (SAN), and their blends, which were reactively compatibilized using a styrene‐acrylonitrile maleic anhydride (SANMA) terpolymer. Transmission electron microscopy (TEM) investigations revealed the phase morphology of the blends, which is characterized by inclusions of the minor component in the matrix of the major phase. The blend with 50% PA 6 and 50% SAN depicted a cocontinuous morphology. Using a microtensile device for TEM, the samples were deformed under uniaxial loading in the “dry” state (characterized by a zero water content in the PA 6 phase) and in a “wet” state (with water in the PA 6 phase). Whereas the dry blends behaved brittle, the wet blends showed a larger ductility with the formation of deformation bands in the matrix (PA 6 or SAN), which were initiated by stress concentration at the SAN and PA 6 particles, respectively. In the interface of blends with a PA 6 matrix and SAN inclusions, two phenomena were observed: partial cavitation and debonding on the one hand and partial fibrillation on the other hand. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

5.
Shu-Lin Bai  Min Wang 《Polymer》2003,44(21):6537-6547
A series of three-phase polymer blends, composed of polypropylene (PP) matrix, polyamide-6 (PA6) fillers and polyethylene-octene elastomer grafted with maleic anhydride (POE-g-MA) modifiers, were designed and manufactured. Their mechanical behavior under cyclic loading-unloading was studied by using a video-controlled testing system named as VideoTraction© system. It was found that with the increasing PA6 and POE content, the strain hardening became more and more prominent, the volume strain decreased, and the energy dissipated increased. A detailed examination of the cryo-fractured surfaces under SEM was undertaken. The microcavity nucleation, growth and coalescence were observed, and represent the main mechanisms of plastic deformation and damage. The high volume strain comes from the abundant formation of microvoids. On the contrary, the formation of microvoids resulted in relatively smaller quantity of energy dissipation. This result coincides well with the toughening mechanisms of polymer blends revealed by other peoples.  相似文献   

6.
The dynamic rheological behavior is measured by small amplitude oscillatory shear on rotational rheometer for polypropylene/polyamide 6 (PP/PA6) blends compatibilized by a polypropylene grafted maleic anhydride (PP‐g‐MAH). Scanning electron microscope (SEM) results show that the PP/PP‐g‐MAH/PA6 (=100/6/40wt) is sea‐island structure, the PP/PP‐g‐MAH/PA6 (=100/6/60wt) blend is semi‐cocontinuous. Coarse PA6 zones can be observed when the weight ratio is 100/6/80. At low frequency the complex viscosity, dynamic modulus of the PP/PP‐g‐MAH/PA6 (PP/PP‐g‐MAH = 100/6wt) blends first increase then drop with the increase of PA6 weight content in the range of 0–100, the maximum value arrives at the weight content of 60. The Cole–Cole plots as well as the weighted relaxation spectra of the blends have a main arc and a tail when the weight ratio of PP/PP‐g‐MAH/PA6 is in the range of 100/6/20–100/6/60, but have different shapes when the weight ratio increases to 100/6/80 and 100/6/100. The possible reason is the weight ratio of 100/6/80 and 100/6/100 is close to the phase inversion point. In fitting the storage modulus data at low frequency, Palierne's model with two parameters interfacial tension and interfacial shear modulus is better than Bousmina's model. Palierne's model with only one parameter of interfacial tension can not fit the data well. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42091.  相似文献   

7.
Ternary blends, based on 70% by weight of polypropylene (PP) with 30% by weight of a dispersed phase, consisting of 15% polyamide-6 (PA6) and 15% of a mixture comprising varying ratios of an unreactive poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) triblock copolymer and a reactive maleic anhydride-grafted SEBS-g-MA, were produced via melt blending in a co-rotating twin-screw extruder. TEM revealed the blend containing only non-reactive SEBS to exhibit individual PA6 and SEBS dispersed phases. However, the progressive replacement of SEBS with reactive SEBS-g-MA increased the degree of interfacial reaction between the SEBS and PA6 phases, thus reducing interfacial tension and providing a driving force for encapsulation of the PA6 by the SEBS. Consequently, the dispersed-phase morphology was observed to transform from two separate phases to acorn-type composite particles, then to individual core-shell particles and finally to agglomerates of the core-shell particles. The resultant blends exhibited significant morphology-induced variations in both thermal and mechanical properties. DSC showed that blends in which the diameter of the PA6 particles was reduced to ≤3 μm by the increasing interfacial reaction exhibited fractionated PA6 crystallisation. In general, mechanical testing showed the blends to exhibit inferior low-strain tensile properties (modulus and yield stress) compared to the matrix PP, but superior ultimate tensile properties (stress and strain at break) and impact strength. These changes are discussed with reference to composite models.  相似文献   

8.
Dean Shi  Guo-Hua Hu  Zhuo Ke  Jinghua Yin 《Polymer》2006,47(13):4659-4666
This paper deals with the dynamic rheological behavior of polypropylene/polyamide6 (PP/PA6) uncompatibilized blends and those compatibilized with a maleic anhydride grafted PP (PP/PP-g-MAH/PA6). The terminal relaxation times of the blends predicted by the Palierne emulsion model were compared with those obtained from experimental relaxation time spectra. The Palierne model succeeded well in describing PP/PA6 uncompatibilized blends with relatively low dispersed phase contents (10 wt%) and failed doing so for those of which the dispersed contents were high (30 wt%). It also failed for the compatibilized ones, irrespective of the dispersed phase content (10 or 30 wt%) and whether or not interface relaxation was taken into consideration. In the case of the uncompatibilized blend with high dispersed-phase content, interconnections among inclusions of the dispersed phase were responsible for the failure of the Palierne model. As for the compatiblized blends, in addition to particle interconnections, the existence of emulsion-in-emulsion (EE) structures was another factor responsible for the failure of Palierne model. A methodology was developed to use Palierne emulsion model upon taking into account the effects of the EE structure on the viscosity of the continuous phase and the effective volume fraction of the dispersed phase.  相似文献   

9.
Polypropylene has many advantages over other polymeric fibers such as high tensile strength, good abrasion resistance, high chemical resistance and very competitive price. However, the use of polypropylene fiber is restricted by the lack of affinity of conventional dyestuffs for this fiber. Many attempts have been made to improve the dyeability of polypropylene by various techniques. It must however, be noted that enhanced dyeability of polypropylene should not adversely impair its other properties, in particular its mechanical properties. To this end, in the present investigation, a mixture experimental design was used in order to attain an optimal region of proportions of three components namely polypropylene (PP), maleated polypropylene (polypropylene grafted with maleic anhydride (MAH-PP) as a compatibilizing agent) and polyamide 6 (PA6); where enhanced dyeability as well as retained mechanical properties would be achieved. Additionally, in order to analyze the morphology of the blends, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used. Finally, in order to evaluate effect of each component on fastness properties of the blends, wash, rub and light fastnesses were determined by the corresponding standard test methods.  相似文献   

10.
Polyamide 6/polypropylene (PA6/PP=70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were prepared using twin screw extruder followed by injection molding. Maleated polypropylene (MAH-g-PP) was used to compatibilize the blend system. The mechanical properties of PA6/PP nanocomposites were studied through tensile and flexural tests. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the fracture surface morphology and the dispersion of the organoclay, respectively. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. The thermal properties were characterized by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dynamic mechanical properties of PA6/PP nanocomposites were analyzed by using dynamic mechanical thermal analyzer (DMTA). The strength and stiffness of PA6/PP nanocomposites were improved significantly in the presence of MAH-g-PP. This has been attributed to the synergistic effect of organoclay and MAH-g-PP. The MAH-g-PP compatibilized PA6/PP nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PA6, PP and organoclay. TEM and XRD results revealed the formation of nanocomposites as the organoclay was intercalated and exfoliated. A possible chemical interaction between PA6, PP, organophilic modified montmorillonite and MAH-g-PP was proposed based on the experimental work.  相似文献   

11.
Blends of isotactic polypropylene (iPP) with the polyamide nylon-6 (N6), prepared by extrusion, were studied with a composition of up to 30% by weight polyamide. In the case of a 70/30 iPP/N6 blend, the influence of a compatibilizing agent based on polypropylene functionalized with maleic anhydride (PP-g-MA), with compositions of 1, 3, 5, and 10% by weight in polypropylene, was followed. The influence of the concentration of N6 and the compatibilizing agent on the rheological and thermal properties, and the morphology of the blends, was analyzed by monitoring the melt viscosity at different shear rates, differential scanning calorimetry, and polarized light microscopy. Vibrational spectroscopy was used to characterize the blends and to study the effect of the compatibilizing agent. The viscosity—composition curves for the iPP/N6 blends, in the composition and shear rate ranges analyzed, show a negative deviation from the additive rule, while the opposite trend is observed for the blends compatibilized with PP-g-MA. Important variations in the spectroscopic behavior was observed between compatibilized and noncompatibilized blends, which varied as a function of the compatibilizing agent concentration. The crystallization rates of iPP in the iPP/N6 blends, under both dynamic and isothermal conditions, are much greater than are those observed for pure iPP and are directly related to the nucleating activity of the polyamide. This effect is much smaller in the presence of the compatibilizing agent. The isothermal crystallization of the polyamide N6 in compatibilized blends is affected by the presence of iPP, reducing the crystallization rate due to the diluent effect of the polypropylene. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2665–2677, 1997  相似文献   

12.
The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry  相似文献   

13.
Blends of polypropylene (PP) and polystyrene (PS) were prepared in a twin-screw extruder and studied in a wide range of compositions. Phase continuity was first determined using selective solvent extraction. Subsequently, dynamic stress rheometry and dynamic mechanical analysis were used to detect the co-continuity and phase inversion compositions in the melt and the solid states. It appears that the phase inversion occurs in a domain rather than at a single point. The evaluation of the storage modulus of PP/PS blends in the melt at a constant low frequency gives information about the co-continuity, as far as the onset of co-continuity and phase inversion composition of the PS phase are concerned. The evaluation of the storage modulus and mechanical loss factor at a constant high temperature, or the glass transition temperature intensity allowed to precisely detect the phase inversion composition. The fractionated or bulk crystallization behavior of the crystallizable PP phase in the PP/PS blends can also be used to identify the matrix/dispersed phase or co-continuous phase morphology. Several semi-empirical models using the dynamic viscoelastic properties of blend components have been applied to detect the phase inversion composition. An extensive data set presented, can also be used to guide future modeling.  相似文献   

14.
A series of polymer blends were designed and manufactured. They are composed of three phases: polypropylene (PP), polyamide-6 (PA6) and polyethylene-octene elastomer (POE) grafted with maleic anhydride. The weight fraction of PA6 was adjusted from 0 to 40% by increments of 10%, and the weight fraction of POE was systematically half that of PA6. The morphology, essentially made of PA6 particles dispersed in the PP matrix, was characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the extruded plates prepared with the blends, the shape of the dispersed PA6 particles showed an elongated ellipsoidal shape, whose aspect ratio increased somehow with alloying content. The POE modifier was observed both as a thin interlayer (less than 100 nm thickness) at the PP/PA6 interface, and as a few isolated particles. The elastic modulus and yield stress in tension are nearly constant for PP and blends. By contrast, the notched Izod impact strength increases very much with alloying content. This remarkable effect is interpreted in terms of POE interphase cavitation, enhanced plastic shear deformation and resistance of PA6 particles to crack propagation.  相似文献   

15.
In this work, in situ investigations of the micromechanical properties of reactively compatibilized blends of polyamide 6 (PA6) and an acrylonitrile–butadiene–styrene copolymer (ABS) were performed with transmission electron microscopy. Three PA6/ABS blends were prepared with a disperse morphology (inclusions of PA6 or ABS) and with a cocontinuous structure. The objective of this work was to study the deformation of the inclusions and the interface between the PA6 phase and the ABS phase. Our transmission electron microscopy investigations revealed that the morphology of the blends was strongly influenced by the asymmetric nature of the interface between PA6 and ABS. In the blends with a PA6 matrix, the interface between PA6 and the ABS inclusions was deformed in tensile deformation under uniaxial loading. A strong influence of the PA6 water content on the (micro)mechanical behavior was observed. Although the “dry” blends behaved in a brittle fashion, the “wet” blends behaved in a ductile fashion with the formation of deformation bands in the matrix (PA6 or ABS), which were initiated by stress concentration at the particles (ABS or PA6, respectively). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
Ke Wang 《Polymer》2007,48(7):2144-2154
In this study, both organoclay and EPDM-g-MA rubber were used to simultaneously improve the toughness and stiffness of polyamide 6 (PA6). We first prepared PA6/EPDM-g-MA/organoclay ternary nanocomposites using melt blending. Then the composites were subjected to traditional injection molding and so-called dynamic packing injection molding. The dispersion of clay, phase morphology, crystallinity and orientation of PA6 as well the mechanical properties were characterized by WAXD, SEM, DSC, 2D-WAXS and mechanical testing, respectively. The effects of clay on phase morphology and mechanical properties of PA6/EPDM-g-MA blends could be summarized as follows: (1) weakening interphase adhesion between PA6 and EPDM-g-MA rubber particles, resulted in increasing of rubber particle size, as the clay and rubber contents are low; (2) preventing coalescence of rubber domains, arisen in decreasing of rubber particle size, as the clay and rubber contents are high; (3) the blocking effect on the overlap of stress volume around rubber particles caused broadening of the brittle-ductile transition region and decrease of toughness, and (4) the effective stress transfer leading a better reinforcement when the interparticle distance is smaller than the critical value.  相似文献   

17.
Within a IUPAC study, melt processing, mechanical, and fatigue crack growth properties of blends of polyamide 6 (PA 6) and poly(acrylonitrile–butadiene–styrene) (ABS) were investigated. We focused on the influence of reactive compatibilization on blend properties using a styrene–acrylonitrile–maleic anhydride random terpolymer (SANMA). Two series of PA 6/ABS blends with 30 wt % PA 6 and 70 wt % PA 6, respectively, were prepared with varying amounts of SANMA. Our experiments revealed that the morphology of the matrix (PA 6 or ABS) strongly affects the blend properties. The viscosity of PA 6/ABS blends monotonically increases with SANMA concentration because of the formation of high‐molecular weight graft copolymers. The extrudate swell of the blends was much larger than that of neat PA 6 and ABS and decreased with increasing SANMA concentrations at a constant extrusion pressure. This observation can be explained by the effect of the capillary number. The fracture resistance of these blends, including specific work to break and impact strength, is lower than that of PA 6 or ABS alone, but increases with SANMA concentration. This effect is most strongly pronounced for blends with 70 wt % PA 6. Fatigue crack growth experiments showed that the addition of 1–2 wt % SANMA enhances the resistance against crack propagation for ABS‐based blends. The correlation between blend composition, morphology and processing/end‐use properties of reactively compatibilized PA 6/ABS blends is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

18.
In this work, typical ternary blends of three versatile polymers—polyamide 6, a propylene–ethylene copolymer (co‐PP), and polystyrene—were studied. As a compatibilizer, co‐PP with randomly dispersed minor ethylene units was multimonomer‐melt‐grafted in the presence of maleic anhydride, styrene, and dicumyl peroxide. The influence of the ethylene content in co‐PP and the blend composition on the performance was investigated. Scanning electron microscopy images showed an obvious decrease in the droplet size of the dispersed phase with increases in the compatibilizer content and number of ethylene units in co‐PP. Peaks of tan δ/temperature curves approaching the glass‐transition temperatures of the components were observed with dynamic mechanical thermal analysis. The improved mechanical properties implied good compatibility of the components in the blends. Significant toughening was achieved when the concentration of co‐PP was increased from 15 to 25 wt %: the elongation at break of the compatibilized blends increased dozens of times in comparison with the elongation at break of the uncompatibilized blends. The introduction of the multimonomer‐melt‐grafted co‐PP was shown to be an effective approach for improving immiscible multipolymer blends and to have practical potential. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

19.
Christian G'Sell  Shu-Lin Bai 《Polymer》2004,45(17):5785-5792
Plastic deformation upon stretching was investigated in ternary blends of polypropylene, polyamide 6 and maleic anhydride-grafted polyethylene-octene elastomer (PP/PA6/POE). A novel video-controlled tensile testing method was utilized, which allows recording simultaneously axial strain, axial stress and volume strain while axial strain-rate is regulated at a constant value even after necking has begun. Increasing the alloying content modifies drastically the original stress-strain properties of PP: yield softening is suppressed and strain hardening is increased. As for the volume strain, which is representative of the overall cavitation process, it is found to decrease with increasing alloying content (apart from a small increase for low alloying content). This unexpected result indicates that the finely dispersed cavities nucleated under tension at the POE interphase of PA6 particles and at isolated POE particles favor the profuse development of plastic shear bands in the PP matrix. As such, it can be considered as an experimental evidence of the synergistic effect of cavitation and shear banding in a structural polymer.  相似文献   

20.
In this article, a novel method has been successfully developed to prepare the anionic polyamide 6/polystyrene (APA6/PS) blends. The macroactivator P(St‐co‐IEM) was synthesized by the free radical polymerization of 2‐isocyanatoethyl methacrylate and styrene (St), then the graft copolymer of PS and APA6 (PS‐g‐APA6) can be obtained by the anionic polymerization of ɛ‐caprolactam activated by the macroactivator P(St‐co‐IEM). The X‐ray diffraction analysis, differential scanning calorimetry, scanning electron microscopy analysis, contact angle measurement, water absorption measurement, molau test, thermogravimetric analysis, and mechanical properties test were performed separately to study the effects of P(St‐co‐IEM) on crystallinity, morphology, water resistance, thermal stability, and mechanical properties. The results indicate the synthesis of macroactivator can promote the formation of the γ‐phase. Moreover, it can improve the interfacial compatibility, water resistance, thermal stability, and toughness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46302.  相似文献   

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